Process of making 3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4,5]decanes

ABSTRACT

3,7,9-Trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes of formula I ##STR1## wherein R 1  and R 2  are independently hydrogen, alkyl, cycloalkyl, bicycloalkyl, tricycloalkyl or aryl; or can be halogen when n or m is zero, 
     R 3 , R 4 , R 5  and R 6  are independently hydrogen, alkyl, aralkyl or aryl; 
     X and Y are independently --O--, --S-- or --NR 16  -- where R 16  is alkyl, cycloalkyl, alkenyl, aryl or aralkyl; 
     W and Z are independently O or S; and 
     n, m, o and p are independently zero or 1, are effective in stabilizing organic materials against the deleterious effects of oxygen, heat and/or actinic radiation.

This is a divisional of Ser. No. 07/843,790, filed on Feb. 27, 1992, nowU.S. Pat. No. 5,187,213, issued on Feb. 16, 1993, which is a divisionalof Ser. No. 07/702,982, filed on May 20, 1991, now U.S. Pat. No.5,132,426, issued on Jul. 21, 1992, which is a continuation-in-part ofSer. No. 07/572,728, filed on Aug. 23, 1990, now U.S. Pat. No.5,075,482, issued on Dec. 24, 1991.

The instant invention pertains to novel substituted3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes and their use asstabilizers for various organic materials subject to the deleteriouseffects of oxygen, heat and/or actinic radiation. The instant compoundsprovide both melt flow stabilization and good resistance againstdiscoloration during polymer processing.

BACKGROUND OF THE INVENTION

U.S. Pat. Nos. 4,751,319; 4,812,501 and 4,831,178 describe aliphatic andaryl esters of 1,3,2-oxazaphospholidines as color improvers and processstabilizers for various polymer substrates.

The instant compounds of this invention are structurally distinguishedfrom the compounds of the prior art, and further provide superiorstabilizing performance as well. This is manifested in the superiorprocessing stabilization of polymeric substrates in terms of melt flowstabilization and resistance to discoloration.

OBJECTS OF THE INVENTION

One object of the instant invention is to provide new substituted3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes which are effectivestabilizers for organic materials subject to oxidative, thermal and/oractinic degradation.

Another object of the invention is to provide stabilized compositionscontaining an effective stabilizing amount of a3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane compound of thisinvention alone or in combination with a hindered phenolic antioxidantand/or a hindered amine thermal stabilizer.

DETAILED DISCLOSURE

The instant invention pertains to substituted3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes of formula I ##STR2##wherein R₁ and R₂ are independently hydrogen; a linear or branched alkylof 1 to 30 carbon atoms; said alkyl optionally terminated with --OR₇,--NR₈ R₉, --SR₁₀, --COOR₁₁ or --CONR₁₂ R₁₃, where R₇, R₈, R₉ and R₁₀ areindependently alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbonatoms, and R₁₁, R₁₂ and R₁₃ are independently hydrogen or the samemeaning as R₇ ; or said alkyl interrupted by one or more --O--, --S--,--SO--, --SO₂ --, --CO--, --COO--, --OCO--, --CONR₁₄, --NR₁₄ CO-- or--NR₁₅ -- where R₁₄ and R₁₅ have the same meaning as R₁₁ ; alkenyl of 3to 20 carbon atoms; aryl of 6 to 10 carbon atoms; said aryl substitutedby one to three substituents selected from the group consisting of alkylof 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkylof 7 to 15 carbon atoms and the group --(CH₂)_(k) COOR₂₀ where k is 0, 1or 2 and R₂₀ is hydrogen, alkyl of 1 to 20 carbon atoms or cycloalkyl of5 to 12 carbon atoms; phenylalkyl of 7 to 9 carbon atoms; bicycloalkylof 7 to 18 carbon atoms; or tricycloalkyl of 10 to 20 carbon atoms; orR₁ and R₂ are independently a group of formula II ##STR3## where E ishydrogen, --OH, alkyl of 1 to 18 carbon atoms, alkenyl of 3 to 18 carbonatoms, aralkyl of 7 to 15 carbon atoms, alkoxy of 1 to 18 carbon atomsor cycloalkoxy of 5 to 12 carbon atoms; and L is --O-- or --NT-- where Tis hydrogen, alkyl of 1 to 18 carbon atoms or cycloalkyl of 5 to 12carbon atoms; or when n or m is zero, R₁ or R₂ is also independently F,Cl, Br or I;

R₃ is hydrogen, alkyl of 1 to 20 carbon atoms, phenylalkyl of 7 to 15carbon atoms or aryl of 6 to 10 carbon atoms;

R₄, R₅ and R₆ are independently hydrogen, alkyl of 1 to 4 carbon atomsor aryl of 6 to 10 carbon atoms;

X and Y are independently --O--, --S-- or --NR₁₆ -- where R₁₆ ishydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, alkenyl of 3 to 18 carbon atoms, aryl of 6 to 10 carbon atoms,said aryl substituted by one or two alkyl of 1 to 4 carbon atoms; orphenylalkyl of 7 to 15 carbon atoms;

W and Z are independently O or S; and

n, m, o and p are independently zero or 1.

When p or o is zero, a lone pair of electrons rests on the P atom. Whenn or m is zero, X or Y is a direct bond.

All of the possible stereoisomers which are predictable, with respect tohaving multiple asymmetric centers at phosphorous and carbon and achiral axis, are deemed to be included within the scope of thisinvention.

Preferably R₁ and R₂ are the same and are alkyl of 1 to 20 carbon atoms,or when n and m are zero, are also Cl- or Br-, or are

a substituted phenyl of formula III ##STR4## wherein R₁₇ and R₁₈ areindependently hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5to 6 carbon atoms or phenylalkyl of 7 to 9 carbon atoms;

R₁₉ is hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 6carbon atoms, phenylalkyl of 7 to 9 carbon atoms or a group --CH₂ CH₂COOR₂₀ wherein R₂₀ wherein R₂₀ is hydrogen or alkyl of 1 to 20 carbonatoms; or

where R₁ and R₂ are cycloalkyl of 5 to 6 carbon atoms; bicycloalkyl of 7to 10 carbon atoms; or tricycloalkyl of 10 to 12 carbon atoms;

R₃ is hydrogen, alkyl of 1 to 20 carbon atoms or phenylalkyl of 7 to 9carbon atoms;

R₄, R₅ and R₆ are each hydrogen;

X and Y are O or S;

n and m are the same and are zero or 1; and

p and o are zero.

Most preferably, R₁ and R₂ are the same and are alkyl of 4 to 18 carbonatoms or a group of formula III wherein

R₁₇ and R₁₈ are hydrogen or alkyl of 4 to 12 carbon atoms,

R₁₉ is hydrogen, alkyl of 4 to 12 carbon atoms or is --CH₂ CH₂ COOR₂₀where R₂₀ is alkyl of 1 to 18 carbon atoms;

R₃ is hydrogen, alkyl of 1 to 18 carbon atoms or benzyl;

R₄, R₅ and R₆ are each hydrogen;

X and Y are --O--;

m and n are 1; and

o and p are zero.

When any of R₁ to R₂₀ is alkyl, such alkyl groups are, for example,methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl,2-ethylhexyl, n-octyl, tert-octyl, lauryl, n-octadecyl, eicosyl andtriacontyl; when said radicals are cycloalkyl, they are, for example,cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl; when said radicalsare alkenyl, they are, for example, allyl, butenyl and oleyl; when saidradicals are phenylalkyl, they are, for example, benzyl, phenethyl,α-methylbenzyl and α,α-dimethylbenzyl; when said radicals are aryl, theyare, for example, phenyl and naphthyl; when said radicals are alkylinterrupted by --O-- or --S--, they are, for example, 3-oxaamyl,3,6-dioxaoctyl, 3-thiaamyl and 3,6-dithiaoctyl; when said radicals arebicycloalkyl or tricycloalkyl, they are, for example, isobornyl andadamantyl.

The compounds of this invention are prepared by the reaction of thecorresponding N-substituted amino-tris(hydroxymethyl)methane andcorresponding substituted dichlorophosphine. The starting N-substitutedamino-tris(hydroxymethyl)methanes and substituted dichlorophosphines areitems of commerce or are readily prepared by known methods.Alternatively, the compounds of this invention are prepared by thereaction of the appropriate nucleophile with the novel1-substituted-2,8-dihalo-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes.The novel1-substituted-2,8-dihalo-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanesare prepared by reaction of a phosphorus trihalide and the appropriateN-substituted amino-tris(hydroxymethyl)methane. These reactions aretypically carried out in an inert hydrocarbon or ether solvent, such astoluene or tetrahydrofuran, in the presence of an acid scavenger, suchas triethylamine, pyridine or poly(4-vinylpyridine). The instantcompounds are preferably prepared by transesterification of thecorresponding N-substituted amino-tris(hydroxymethyl)methane and atrialkyl or triaryl phosphite. The transesterifications are preferablycarried out in the presence of an alkali metal amide, alkoxide orphenoxide catalyst such as sodium phenoxide, sodium methoxide or lithiumamide. Optionally a solvent such as tetraethylene glycol dimethyl ether;2,4-di-tert-butylphenol; C₁₀ -C₂₀ n-alkanes, isoalkanes, aralkanes orcycloalkanes; decalin; or regular mineral spirits such as UnionChemicals AMSCO Solvent 1005 may be employed.

The instant invention also relates to a facile preferred process formaking the compounds of formula I which comprises transesterifying acompound of formula IV ##STR5## with an essentially stoichiometricamount of a trialkyl or triaryl phosphite of the formula (R₁ O)₃ P or(R₂ O)₃ P or mixture thereof in the presence of an alkali metal amide,alkoxide or phenoxide catalyst, wherein R₁ to R₆ are as defined above.

The instant invention also pertains to a stabilized composition whichcomprises

(a) an organic material subject to oxidative, thermal or actinicdegradation, and

(b) an effective stabilizing amount of a compound of formula I asdescribed above.

The organic material of component (a) is preferably a synthetic polymer;most preferably a polyolefin.

Substrates in which the compounds of this invention are particularlyuseful are polyolefins such as polypropylene and polyethylene;polystyrene, including especially impact polystyrene; ABS resin;elastomers such as e.g. butadiene rubber, EPM, EPDM, SBR and nitrilerubber.

The instant invention also pertains to stabilized compositions whichadditionally contain a phenolic antioxidant or a hindered amine compoundor a combination thereof. Lists of appropriate phenolic antioxidants andof hindered amine compounds are given below.

Substrates in which the compounds of this invention are particularlyuseful are polyolefins such as polyethylene and polypropylene;polystyrene, including especially impact polystyrene; ABS resin;elastomers such as e.g. butadiene rubber, EPM, EPDM, SBR and nitrilerubber; and lubricating oils.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, aswell as polymers of cycloolefins, for instance of cyclopentene ornorbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbornene.

4. Polystyrene, poly-(p-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, a diene polymer oran ethylene/propylene/diene terpolymer, and block polymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate, vinylidene chloride/vinyl acetate copolymers, or vinylfluoride/vinyl ether copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other orother unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal hydroxyl groups on the one side andaliphatic or aromatic polyisocyanates on the other side, as well asprecursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenyleneterephthalamide or poly-m-phenylene isophthalamide, as well ascopolymers thereof with polyethers, such as for instance withpolyethylene glycol, polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane]terephthalate andpolyhydroxybenzoates as well as block-copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.

28. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

31. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.5 to about 2%, and especially 0.1 toabout 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert.butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol.

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

4,4'-thio-bis-(6-tert-butyl-2-methylphenol).

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt.

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

methanol

octadecanol

1,6-hexanediol

neopentyl glycol

thiodiethylene glycol

diethylene glycol

triethylene glycol

pentaerythritol

tris-hydroxyethyl isocyanurate

di-hydroxyethyl oxalic acid diamide.

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

methanol

octadecanol

1,6-hexanediol

neopentyl glycol

thiodiethylene glycol

diethylene glycol

triethylene glycol

pentaerythritol

tris-hydroxyethyl isocyanurate

di-hydroxyethyl oxalic acid diamide.

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

1.10 Diarylamines, for example, diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,4,4'-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product ofdiphenylamine and 2,4,4-trimethylpentene, reaction product ofN-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers.

2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-,3',5'-bis-(α,α-dimethylbenzyl),3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearylsorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one) andbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecaneor bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

The stabilizers of the instant invention have good hydrolytic stability.However, co-additives can optionally be employed to improve theirhydrolytic stability still further. Examples of such co-stabilizers are:

Nitrogen containing compounds such as those described in U.S. Pat. Nos.3,553,298 and 4,116,926, the disclosures of which are herebyincorporated by reference;

Long-chain aliphatic amines such as those disclosed in U.S. Pat. Nos.4,650,894 and 4,707,509, the disclosures of which are herebyincorporated by reference; and

Organic acid metal salts such as those described in U.S. Pat. Nos.4,086,304 and 4,402,858, the disclosure of which are hereby incorporatedby reference.

The nitrogen compounds of particular interest are amines which have beenshown to improve the hydrolytic stability of pentaerythritol spiro bisphosphites as taught in U.S. Pat. No. 4,888,371 where it is disclosedthat an aliphatic, cycloaliphatic or heterocyclic amine as disclosed inU.S. Pat. Nos. 3,553,298 and 4,116,926 can be added to a spiro bisphosphite to improve hydrolytic stability.

Exemplary amines include, for example, trialkanolamines such astriethanolamine, triisopropanolamine and tri-n-propanolamine;dialkanolamines such as diethanol dodecylamine, diethanoloctadecylamine, diethanol oleylamine, diethanol octylamine, diethanolhexadecylamine, diisopropanol dodecylamine, diisopropanol octadecylamineand di-n-propanol octadecylamine; dialkanolamines such asdiisopropanolamine and diethanolamine; alkane-bis(dialkanolamines) suchas ethylene-bis(diethanolamine) and ethylene-bis(diisopropanolamine);heterocyclic amines such as hexamethylenetetramine, piperidine,pyrrolidine, N-methylpiperidine, N-methylpyrrolidine, oxazolidine,morpholine and isooxazolidine; and amine oxides such aslauryldimethylamine oxide and stearyldimethylamine oxide.

The preferred amount of the amine is from 0.01 to 5 parts by weight,preferably from 0.1 to 2 parts by weight, per 100 parts by weight of thespiro bis phosphite.

The following examples are presented for the purpose of illustrationonly and are not to be construed to limit the nature or scope of theinstant invention in any manner whatsoever.

EXAMPLE 11-Benzyl-2,8-bis(2,6-di-tert-butyl-4-methylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

Into a solution of 5 g (24.0 mmol) ofN-benzylamino-tris(hydroxymethyl)methane and 13.2 mL (9.6 g, 95.0 mmol)of triethylamine in 140 mL of toluene is added dropwise 15.23 g (47.0mmol) of 2,6-di-tert-butyl-4-methylphenoxydichlorophosphine at 0° C.After the addition is complete, the reaction mixture is allowed to warmto ambient temperature. After 25 hours, an additional 0.76 g (2.30 mmol)of 2,6-di-tert-butyl-4-methylphenoxydichlorophosphine and 0.66 mL (4.70mmol) of triethylamine are added to the reaction mixture. One hour afterthe second addition, the reaction mixture is filtered and the filtrateis concentrated in vacuo to give 20 g of a thick gel. The residue ispurified by flash chromatography, using silica gel and a mixture of 97%hexane/2% ethyl acetate/1% triethylamine (by volume) as an eluent, togive 5.9 g (35% yield) of a white solid melting at 81°-85° C.

Analysis: Calcd for C₄₁ H₅₉ NO₅ P₂ : C, 69.6; H, 8.4; N, 2.0. Found: C,69.8; H, 8.6; N, 1.7.

EXAMPLE 21-Dodecyl-2,8-bis(2,6-di-tert-butyl-4methylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro-[4.5]decane

The procedure of Example 1 is repeated using 4.5 g (15.5 mmol) ofN-dodecylamino-tris(hydroxymethyl)methane and 8.7 mL (62.2 mmol) oftriethylamine in 150 mL of toluene and 10 g (31.1 mmol) of2,6-di-tert-butyl-4-methylphenoxydichlorophosphine to give 12.8 g of ayellow oil. The residue is purified by flash chromatography, usingsilica gel and a mixture of 97.5% hexane/1.5% ethyl acetate/1%triethylamine (by volume) as a solvent system, to give 10.1 g (83%yield) of a white solid melting at 45°-50° C.

Analysis: Calcd for C₄₆ H₇₇ NO₅ P₂ : C, 70.3; H,9.9; N, 1.8. Found: C,70.5; H, 10.3; N, 1.6.

EXAMPLE 3 1-(H)-2,8-Bis(2,6-di-tert-butyl-4-methylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 1 is repeated using 1.74 g (14.4 mmol) oftris(hydroxymethyl)aminomethane, 8.07 mL (5.86 g, 58.0 mmol) oftriethylamine, 9.31 g (28.9 mmol) of2,6-di-tert-butyl-4-methylphenoxydichlorophosphine to give 10.5 g of acrude oil. The residue is purified by trituration with hexane to give3.32 g (37% yield) of an off-white solid melting at 192°-196° C.

Analysis: Calcd for C₃₄ H₅₃ NO₅ P₂ : C, 66.1; H, 8.7; N, 2.3. Found: C,66.1; H, 8.8; N, 2.1.

EXAMPLE 41-Benzyl-2,8-bis[2,6-di-tert-butyl-4-(2-methoxycarbonylethyl)-phenoxy]-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 1 is repeated using 5.48 g (26 mmol) ofN-benzylamino-tris(hydroxymethyl)methane, 19.6 g (27 mL, 194 mmol) oftriethylamine, 20.44 g (52 mmol) of2,6-di-tert-butyl-4-(methylpropion-3-yl)phenoxydichlorophosphine and 125mL of toluene to give 26.8 g of a crude oil. The residue is purified byflash chromatography (silica gel, 90% hexane/9% ethyl acetate/1%triethylamine) to give 13.58 g (62% yield) of a white solid melting at59°-64° C.

Analysis: Calcd for C₄₇ H₆₇ NO₉ P₂ : C, 66.3; H, 7.9; N, 1.6. Found: C,66.1; H, 8.0; N, 1.6.

EXAMPLE 51-(H)-2,8-Bis(2,4-di-tert-butylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 1 is repeated using 6.37 g (53 mmol) oftris(hydroxymethyl)aminomethane, 32.23 mL (231 mmol) of triethylamine in200 mL of toluene and 32.28 g (105 mmol) of2,4-di-tert-butylphenoxydichlorophosphine in 100 mL of toluene to give35 g of a crude oil. The residue is purified by trituration with hexaneto gave 8.69 g (28% yield) of a white solid melting at 154°-159° C.

Analysis: Calcd for C₃₂ H₄₉ NO₅ P₂ : C, 65.2; H, 8.4; N, 2.4. Found: C,65.2; H, 8.4; N, 2.3.

EXAMPLE 61-Benzyl-2,8-bis(2,4-di-tert-butylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 1 is repeated using 3.76 g (17.8 mmol) ofN-benzylamino-tris(hydroxymethane, 10.92 mL (78.0 mmol) of triethylaminein 150 mL of toluene and 10.93 g (35.6 mmol) of2,4-di-tert-butylphenoxydichlorophosphine in 50 mL of toluene to give24.18 g of a crude oil. Upon purification (silica gel, 96.5% hexane/2%ethyl acetate/1.5% triethylamine), 6.75 g (56% yield) of a white solidmelting at 62°-70° C. is obtained.

Analysis: Calcd for C₃₉ H₅₅ NO₅ P₂ : C, 68.9; H, 8.2; N, 2.1. Found: C,69.1; H, 8.5; N, 2.1.

EXAMPLE 71-(H)-2,8-Bis[2,6-di-tert-butyl-4-(2-n-octadecyloxycarbonyl-ethyl)phenoxy]-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 1 is repeated using 6.06 g (50 mmol) oftris(hydroxymethyl)aminomethane, 30.6 mL (220 mmol) of triethylamine in300 mL of toluene and 63.2 g (100 mmol) of2,6-di-tert-butyl-4-(2-n-octadecyloxycarbonylethyl)phenoxydichlorophosphinein 200 mL of toluene. Upon purification (silica gel, 94% hexane/5% ethylacetate/1% triethylamine) of 50 g of the crude oil, 21.47 g (34% yield)of a white solid melting at 95°-98° C. is obtained.

Analysis: Calcd for C₇₄ H₁₂₉ NO₉ P₂ : C, 71.8; H, 10.5; N, 1.1. Found:C, 71.7; H, 10.6; N, 1.1.

EXAMPLE 81-Isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

Into a solution of 23.24 g (14.8 ml, 169 mmol) of phosphorus trichloridein 420 mL of tetrahydrofuran (THF) is added dropwise a solution of 15 g(84.6 mmol) of N-isobutylaminotris(hydroxymethyl)methane and 26.77 g(27.44 mL, 338.4 mmol) of pyridine in 84 mL of THF at -65° C. to -50° C.over a one-hour period of time. After the addition is complete, thereaction mixture is allowed to warm to ambient temperature. After 24hours of stirring at ambient temperature, the reaction mixture isfiltered and the filtrate is concentrated to an oil. The crude oil ispurified by distillation to give 17.55 g (68% yield) of a white solid:b.p. 110° C. at 0.01 mmHg.

EXAMPLE 91-(H)-2,8-Dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 8 is repeated using 17.4 mL (200 mmol) ofphosphorus trichloride, 12.1 g (100 mmol) oftris(hydroxymethyl)aminomethane and 32.4 mL (400 mmol) of pyridine in500 mL of acetonitrile to give 16.2 g (65% yield) of a clear oil: ³¹ PNMR (C₆ D₆): 175,143 ppm.

EXAMPLE 101-Isobutyl-2,8-di(1-adamantyloxy)-3,7,9-trioxa-1-aza-diphosphaspiro[4.5]decane

Into a solution of 7.53 g (24.6 mmol) of1-isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane(compound of Example 8) in 120 mL of toluene is added dropwise asolution of 7.49 g (49.2mmol) of 1-adamantanol and 5.47 g (7.5 mL, 54.1mmol) of triethylamine in 70 mL of toluene at -60° to -50° C. over a45-minute period. After the addition is complete, the reaction mixtureis allowed to warm to ambient temperature. After two hours, the reactionmixture is filtered and the filtrate is concentrated in vacuo to give13.85 g of a crude oil. The residue is purified by flash chromatography(basic alumina, 97% hexane/3% ethyl acetate) to give 7.87 g (60% yield)of a white solid melting at 97°-100° C.

Analysis: Calcd for C₂₈ H₄₅ NO₅ P₂ : C, 62.6; H, 8.4; N, 2.6. Found: C,62.6; H, 8.8; N, 2.3.

EXAMPLE 111-Isobutyl-2,8-di(n-octadecyloxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 10 is repeated using 10.89 g (36 mmol) of1-isobutyl-2,8-dichloro-3,7,9-trioxa-1aza-2,8-diphosphaspiro[4.5]decane(compound of Example 8) in 200 mL of toluene and 19.25 g (77 mmol) ofn-octadecanol and 7.92 g (10.9 mL, 78 mmol) of triethylamine in 100 mLof toluene to give 26.34 g of white solid. The residue is purified byflash chromatography (basic alumina, 3% ethyl acetate/97% hexane) togive 9.23 g (34% yield) of a white solid melting at 33°-39° C. Theproduct is identified by mass spectroscopy: m/z=773.

EXAMPLE 121-Isobutyl-2,8-bis(2,4-di-tert-butylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 10 is repeated using 3.65 g 12 mmol) of1-isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane(compound of Example 8), 4.92 g (24 mmol) of 2,4-di-tert-butylphenol and3.35 mL of triethylamine in 40 mL of THF to give 8 g of an amber oil.The residue is purified by flash chromatography (silica gel, 97%hexane/2% ethyl acetate/1% triethylamine) to give 2.86 g (37% yield) ofa white solid melting at 66°-69° C.

Analysis: Calcd for C₃₆ H₅₇ NO₅ P₂ : C, 67.0; H, 8.9; N, 2.2. Found: C,67.3; H, 9.3; N, 2.3.

EXAMPLE 131-(H)-2,8-Di(4-tert-octylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 10 is repeated using 15 g (60mmol) of1-(H)-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphoshpaspiro[4,5]decane(compound of Example 9), 24.76 g (120 mmol) of 4-tert-octylphenol and16.7 mL (120 mmol) of triethylamine in 200 mL of THF to give 40 g of aviscous oil. The residue is purified by crystallization from a mixtureof 40 mL of ethanol and 2 mL triethylamine to give 1.7 g (5% yield) of awhite solid melting at 102°-105° C.

Analysis: Calcd for C₃₂ H₄₉ NO₅ P₂ : C, 65.2; H, 8.4; N, 2.4. Found: C,65.1; H, 8.4; N, 2.6.

EXAMPLE 141-Benzyl-2,8-diphenyl-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 1 is repeated using 8.85 g (42 mmol) ofN-benzylamino-tris-(hydroxymethyl)methane, 11.4 mL (84 mmol) ofdichlorophenylphospine and 26 mL (184 mmol) of triethylamine in 200 mLof toluene to give 18 g of a viscous oil. The product is identified bymass spectroscopy: m/z=423.

EXAMPLE 151-Isobutyl-2,8-di(n-octadecylthio)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 10 is repeated using 8.72 g (28.5 mmol) of1-isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane,16.33 g (57 mmol) of n-octadecyl mercaptan and 8.74 mL (63 mmol) oftriethylamine in 200 mL of toluene. A white solid (7.11 g) is isolated.The product is identified by mass spectroscopy: m/z=805.

EXAMPLE 161-Isobutyl-2,8-bis(dicyclohexylamino)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 10 is repeated using1-isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane,dicyclohexylamine and triethylamine in toluene to afford the desiredproduct.

EXAMPLE 171-Isobutyl-2,8-di{2-tert-butyl-4-[2-(isooctyloxycarbonyl)ethyl]-phenoxy}-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The general procedure of Example 10 is repeated using 3.0 g (9.8 mmol)of1-isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane,6.6 g (19.8 mmol) of 2-tert-butyl-4-[2-(isooctyloxycarbonyl)ethyl]phenoland 2.8 mL (19.8 mmol) of triethylamine in 50 mL of toluene at ambienttemperature to give 9.3 g of a colorless oil. The residue is purified byflash chromatography (silica gel; 90.2% hexane: 8.3% ethyl acetate: 1.5%triethylamine) to give the title compound in a yield of 8.1 g (90%) as acolorless oil.

Analysis: Calcd for C₅₀ H₈₁ NO₉ P₂ : C, 66.6; H, 9.1; N, 1.6. Found: C,67.0; H, 9.5; N, 1.6.

EXAMPLE 181-Benzyl-2,8-diphenoxy-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

A mixture of 5.0 g (23.7 mmol) ofN-benzylamino-tris(hydroxymethyl)methane, 12.5 mL (47.4 mmol) oftriphenyl phosphite and 0.09 g (0.71 mmol) of sodium phenolate is heatedto 110°-118° C. at 9-10 mm Hg removing phenol as it forms. The titlecompound is formed in a yield of 10.7 g as a white solid and isidentified by mass spectrometry: m/z=455.

EXAMPLE 191-Isobutyl-2,8-diphenyl-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

Into a solution of 10.0 g (32.7 mmol) of1-isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane,the compound of Example 8, in 60 mL of tetrahydrofuran (THF) is addeddropwise 32.7 mL (65.4 mmol) of a 2M solution of phenyl magnesiumchloride in THF at ambient temperature. The title compound is isolatedin a yield of 11 g as an oil and identified by mass spectrometry:m/z=389.

EXAMPLE 201-Isobutyl-2,8-bis[di(2-ethylhexyl)amino]-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 10 is repeated using 5.0 g (16.4 mmol) of1-isobutyl-2,8-dichloro-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane,the compound of Example 8, 7.9 g (32.8 mmol) of di-2-ethylhexylamine and4.6 mL (32.8 mmol) of triethylamine in 120 mL of toluene. The titlecompound is isolated in a yield of 10.2 g as an oil and is identified bymass spectrometry: m/z=715.

EXAMPLE 211-Isobutyl-2,8-di(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yloxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 10 is repeated using 4.4 g (14.4 mmol) of1-isobutyl-2,8-dichloro-3,7,9-trioxa-2,8-diphosphaspiro[4.5]decane,compound of Example 8, 5.4 g (28.8 mmol) of1-methoxy-2,2,6,6-tetramethyl-4-hydroxypiperidine and 4 mL (28.8 mmol)of triethylamine in 250 mL of toluene to give 10.3 g of a crude oil. Theresidue is purified by flash chromatography (silica gel; 6% ethylacetate:2% triethylamine:92% hexane) to give 3.0 g (34% yield) of thetitle compound.

Analysis: Calcd for C₂₈ H₅₅ N₃ O₇ P₂ : C, 55.3; H, 9.1; N, 6.9. Found:C, 55.1; H, 9.5; N, 6.7.

EXAMPLE 221-Ethyl-2,8-di(2,4-di-tert-butylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The procedure of Example 1 is repeated using 8.0 g (54 mmol) ofN-ethylamino-tris(hydroxymethyl)methane, 30 mL (2.6 mmol) oftriethylamine and 33.2 g (108 mmol) of2,4-di-tert-butylphenoxydichlorophosphine in 320 mL of toluene to give34.4 g of a crude oil. The residue is purified by flash chromatography(silica gel; 1.5% ethyl acetate: 1.5% triethylamine:978% hexane) to give8.7 g of the title compound as an off-white solid.

Analysis: Calcd for C₃₄ H₅₃ NO₅ P₂ : C, 66.1; H, 8.7; N, 2.3. Found: C,66.2; H, 8.8; N, 2.1.

EXAMPLE 231-Benzyl-2,8-di(2,4-di-tert-butylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The general procedure of Example 18 is repeated using 1.5 g (7.1 mmol)of N-benzylamino-tris(hydroxymethyl)methane, 9.2 g (14.2 mmol) oftris(2,4-di-tert-butylphenyl) phosphite and 0.04 g (0.71 mmol) of sodiummethoxide. The title compound is isolated by crystallization fromisopropanol as a white solid and is identified by ³¹ P NMR.

³¹ P NMR (200 MHz)(Benzene-d₆)(ppm): 142.5; 112.2.

The product is accompanied by variable amounts of4-benzylamino-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane identified by³¹ P NMR (200 MHz)(Benzene-d₆)(ppm):91.08; and by mass spectrometry:m/z=239.

EXAMPLE 241-Benzyl-2,8-di(2,4-di-tert-butylphenoxy)-3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decane

The product of Example 18 is reacted with two equivalents of2,4-di-tert-butylphenol and sodium methoxide at reduced pressure and atan elevated temperature to afford the title compound.

EXAMPLE 25 Process Stabilization of Polypropylene at 525° F. (274° C.)

The base formulation comprises unstabilized, old technologypolypropylene (PROFAX 6501, Himont) containing 0.075% by weight ofcalcium stearate. The test additives are incorporated into thepolyproyplene by dry blending or, when the additive is a liquid, using aminimum amount of methylene chloride solvent. The solvent is thenremoved by evaporation under reduced pressure. The stabilized resinformulation is extruded at 90 rpm from a 1 inch (2.54 cm) diameterextruder at 525° F. (274° C.) with a residence time of 90 seconds.

After each of the first and fifth extrusions, the melt flow rate (ingrams/10 minutes) is determined by ASTM method D1238 on the pelletsobtained from the extruder. The results are given in the table below.

    ______________________________________                                               Concentration                                                                              Melt Flow after Extrusion                                 Additive*                                                                              (% by weight)  1         5                                           ______________________________________                                        None     --             10.3      44.3                                        AO A     0.075          4.4       10.7                                        Compound of                                                                            0.075          2.8       4.0                                         Example 1                                                                     Compound of                                                                            0.075          2.7       3.9                                         Example 2                                                                     Compound of                                                                            0.075          3.1       4.4                                         Example 3                                                                     Compound of                                                                            0.075          2.9       4.7                                         Example 4                                                                     Compound of                                                                            0.075          2.8       5.9                                         Example 5                                                                     Compound of                                                                            0.075          2.9       6.4                                         Example 6                                                                     Compound of                                                                            0.075          3.0       4.5                                         Example 12                                                                    ______________________________________                                         *AO A is neopentanetetrayl                                                    tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate).                      

These results show that the substituted3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes provide improved meltflow stabilization to polypropylene compared to the phenolicantioxidant.

EXAMPLE 26 Color Stabilization of Polypropylene

This example illustrates the color stabilizing effectiveness of theinstant compounds in combination with a phenolic antioxidant inpolypropylene.

Using the procedure described in Example 25, polypropylene containing aphenolic antioxidant in combination with an instant compound is extrudedinto pellets. Using the pellets obtained after each of the first andthird extrusions as described in Example 17, the pellets are compressionmolded into 125 mil (3.2 mm) thick plaques at 193° C. Specimenyellowness index (YI) values are determined according to ASTM methodD1925. Lower YI values indicates less discoloration. The results alongwith melt flow values are given in the table below.

    ______________________________________                                                        Melt Flow Values                                                                           Yellowness YI                                    Concent.        after Extrusion                                                                            after Extrusion                                  Additive*                                                                             (% by wt)   1       3      1     3                                    ______________________________________                                        AO A    0.075       4.4     8.0    9.5   8.8                                  AO A plus                                                                             0.075       2.7     3.6    6.9   8.6                                  Example 1                                                                             0.075                                                                 Compound                                                                      AO A plus                                                                             0.075       3.0     3.4    7.3   8.6                                  Example 2                                                                             0.075                                                                 Compound                                                                      AO A plus                                                                             0.075       2.7     3.6    6.4   8.2                                  Example 4                                                                             0.075                                                                 Compound                                                                      AO A plus                                                                             0.075       2.7     3.9    7.0   8.4                                  Example 6                                                                             0.075                                                                 AO A plus                                                                             0.075       3.0     3.4    6.5   8.0                                  Example 12                                                                            0.075                                                                 ______________________________________                                         *AO A is neopentanetetrayl                                                    tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate).                      

The combination of a phenolic antioxidant plus an instant compoundprovides excellent melt flow stabilization and better colorstabilization than does the use of a phenolic antioxidant alone.

EXAMPLE 27

Following the general procedure of Example 25, the effectiveness of theinstant compounds for providing melt flow stabilization to polypropylenecontaining a hindered amine coadditive is determined.

    ______________________________________                                                Concentration                                                                             Melt Flow after Extrusion                                 Additive* (% by weight) 1         5                                           ______________________________________                                        HA 1      0.075         20.6      109                                         HA 1 plus 0.075         5.3       10.1                                        Example 1 0.075                                                               Compound                                                                      HA 1 plus 0.075         5.6       10.2                                        Example 3                                                                     Compound                                                                      ______________________________________                                         *HA 1 is condensation product of                                              N,Nbis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-diamine and            2,4dichloro-6-tert-octylamino-s-triazine.                                

The addition of an instant compound to polypropylene containing ahindered amine compound results in much improved melt flow stabilizationfor the stabilized polypropylene.

EXAMPLE 28 Long Term Heat Aging Stabilization of Polypropylene

Extruded pellets (of Example 26), after the first pass, are compressionmolded into 125 mil (3.2 mm) plaques at 450° F. (232° C.) and then ovenaged at 150° C. in a forced draft oven. The time, in days, to reach ayellowness index (YI) color of 50 units is deemed to represent failure.The results are given in the table below.

    ______________________________________                                                     Concentration                                                    Additive*    (% by weight)                                                                             Days to Failure                                      ______________________________________                                        AO A         0.075       23                                                   AO A plus    0.075       43                                                   Example 1    0.075                                                            Compound                                                                      AO A plus    0.075       32                                                   Example 2    0.075                                                            Compound                                                                      AO A plus    0.075       33                                                   Example 3    0.075 -Compound                                                  AO A plus    0.075       40                                                   Example 4    0.075                                                            Compound                                                                      AO A plus    0.075       40                                                   Example 5    0.075                                                            Compound                                                                      ______________________________________                                         *AO A is neopentanetetrayl                                                    tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate).                      

The combination of an instant compound plus a phenolic antioxidantnearly doubles the long term heat aging stability of the stabilizedpolypropylene over that of the phenolic antioxidant alone.

EXAMPLE 29 Long Term Heat Aging Stability of Polypropylene

Extruded pellets (of Example 27), after the first pass, are compressionmolded into 40 mil (1.0 mm) plaques at 450° F. (232° C.) and then ovenaged at 135° C. in a forced draft oven. The time, in days, to physicalfailure is determined by a 90° bend test. The results are shown in thetable below.

    ______________________________________                                                     Concentration                                                    Additive*    (% by weight)                                                                             Days to Failure                                      ______________________________________                                        HA 1         0.075        3                                                   HA 1 plus    0.075       30                                                   Example 1    0.075                                                            Compound                                                                      HA 1 plus    0.075       26                                                   Example 3    0.075                                                            Compound                                                                      ______________________________________                                         *HA 1 is condensation product of                                              N,Nbis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-diamine and            2,4dichloro-6-tert-octylamino-s-triazine.                                

The addition of an instant compound to polypropylene stabilized with ahindered amine compound increases the long term aging stability of thestabilized polypropylene by nearly an order of magnitude.

EXAMPLE 30 Process Stabilization of Polypropylene at 525° F. (274° C.)

The base formulation comprises unstabilized polypropylene (PROFAX 6501,Himmont) containing 0.075% by weight of calcium stearate. The testadditives are incorporated into the polypropylene by dry blending or,when the additive is a liquid, using a minimum amount of methylenechloride solvent. The solvent is then removed by evaporation underreduced pressure. The stabilized resin formulation is extruded at 90 rpmfrom a 1 inch (2.54 cm) diameter extruder at 525° F. (274° C.) with aresidence time of 90 seconds.

After each of the first and fifth extrusions, the melt flow rate (ingrams/10 minutes) is determined by ASTM method D1238 on the pelletsobtained from the extruder. The results are given in the table below.

    ______________________________________                                               Concentration                                                                              Melt Flow after Extrusion                                 Additive*                                                                              (% by weight)  1         5                                           ______________________________________                                        None     --             11.1      91.5                                        AO A     0.075          6.3       20.8                                        Compound of                                                                            0.075          7.2       28.6                                        Example 7                                                                     Compound of                                                                            0.075          6.5       68.6                                        Example 10                                                                    Compound of                                                                            0.075          5.9       66.4                                        Example 11                                                                    Compound of                                                                            0.075          4.2       28.2                                        Example 13                                                                    ______________________________________                                         *AO A is neopentanetetrayl                                                    tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate).                      

These results show that the substituted3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes provide improved meltflow stabilization to new technology polypropylene compared to thephenolic antioxidant after the first extrusion.

EXAMPLE 31 Process Stabilization of Polypropylene at 525° F. (274° C)

Following the procedure of Example 30, polypropylene containing aphenolic antioxidant in combination with an instant compound is extrudedand the melt flow rate (in grams/10 minutes) determined by ASTM methodD1238 on the pellets obtained from the extruder after each of the firstand fifth extrusions. The results are given in the table below.

    ______________________________________                                                                Melt Flow Values                                                Concent.      after Extrusion                                       Additive*   (% by wt)       1       5                                         ______________________________________                                        AO A        0.075           6.3     20.8                                      AO A plus   0.075           5.1     10.7                                      Example 7   0.075                                                             Compound                                                                      AO A plus   0.075           4.2     7.9                                       Example 10  0.075                                                             Compound                                                                      AO A plus   0.075           3.9     7.2                                       Example 11  0.075                                                             Compound                                                                      AO A plus   0.075           3.8     11.3                                      Example 13  0.075                                                             ______________________________________                                         *AO A is neopentanetetrayl                                                    tetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate).                      

The combination of a phenolic antioxidant plus an instant compoundprovides excellent melt flow stabilization; better stabilization thanobtained by the use of a phenolic antioxidant alone.

What is claimed is:
 1. A process for the preparation of a compound whichis a substituted 3,7,9-trioxa-1aza-2,8-diphosphaspiro[4.5]decane offormula I ##STR6## wherein R₁ and R₂ are independently hydrogen; alinear or branched alkyl of 1 to 30 carbon atoms; said alkyl optionallyterminated with --OR₇, --NR₈ R₉, --SR₁₀, --COOR₁₁ or --CONR₁₂ R₁₃, whereR₇, R₈, R₉ and R₁₀ are independently alkyl of 1 to 20 carbon atoms oralkenyl of 3 to 18 carbon atoms, and R₁₁, R₁₂ and R₁₃ are independentlyhydrogen or the same meaning as R₇ ; or said alkyl interrupted by one ormore --O--, --S--, --SO--, --SO₂ --, --CO--, --COO--, --OCO--, --CONR₁₄,--NR₁₄ CO-- or --NR₁₅ -- where R₁₄ and R₁₅ have the same meaning as R₁₁; alkenyl of 3 to 30 carbon atoms; aryl of 6 to 10 carbon atoms; saidaryl substituted by one to three substitutents selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms and the group--(CH₂)_(k) COOR₂₀ where k is 0, 1 or 2 and R₂₀ is hydrogen, alkyl of 1to 20 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of7 to 9 carbon atoms; bicycloalkyl of 7 to 18 carbon atoms; ortricycloalkyl of 10 to 20 carbon atoms; or R₁ and R₂ are independently agroup of formula II ##STR7## where E is hydrogen, --OH, alkyl of 1 to 18carbon atoms, alkenyl of 3 to 18 carbon atoms, aralkyl of 7 to 15 carbonatoms, alkoxy of 1 to 18 carbon atoms or cycloalkoxy of 5 to 12 carbonatoms; and L is --O-- or --NT-- where T hydrogen, alkyl of 1 to 18carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or when n or m iszero, R₁ or R₂ is also independently F, CI, Br or I;R₃ is hydrogen,alkyl of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms oraryl of 6 to 10 carbon atoms; R₄, R₅ and R₆ are independently hydrogen,alkyl of 1 to 4 carbon atoms or aryl of 6 to 10 carbon atoms; X and Yare indepedently --0--, --S-- or --NR₁₆ -- where R₁₆ is hydrogen, alkylof 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of3 to 18 carbon atoms, aryl of 6 to 10 carbon atoms, said arylsubstituted by one or two alkyl of 1 to 4 carbon atoms; or phenylalkylof 7 to 15 carbon atoms; W and Z are independently O or S; and n, m, oand p are independently zero or 1, which comprises transesterifying acompound of formula IV ##STR8## with an essentially stoichiometricamount of a trialkyl or triaryl phosphite of the formula (R₁ O)₃ P or(R₂ O)₃ P or mixture thereof in the presence of an alkali metal amide,alkoxide or phenoxide catalyst, wherein R₁ to R₆ are as defined above.2. A process according to claim 1 wherein the process is carried out inthe presence of an inert solvent.